FR2683534A1 - NOVEL CATIONIC POLYMERS, THEIR PREPARATION AND THEIR USE. - Google Patents

Abstract

The subject of the invention is a cationic polymer comprising at least one residue of formula I (CF DRAWING IN BOPI) in which the symbols have various meanings, and their use in particular for the manufacture of paper.

Description

The subject of the present invention is novel cationic polymers, their

preparation and

their usage.

  The invention relates in particular to a cationic polymer comprising at least one residue of formula I + 1 + 1 + 1 -CO-NR 2 -CHR 3 -NR 4 Rs (X-NR 6 1R 7 1) -X-NR 8 R Wherein R 2 is hydrogen or R 4 is defined below; R 3 is hydrogen or C 1 -C 3 alkyl; R 4 and R 5 are independently a group; C 1 -C 6 alkyl, cycloalkyl, C 2 -C 6 alkenyl, aryl or aralkyl, said groups being optionally substituted with at least one group selected from C 1 -C 6 hydroxyalkyl, C 1 -C 6 aminoalkyl 6, C 1 -C 6 sulfoalkyl and C 1 -C 6 carboxyalkyl, the carboxy and sulfo groups, when present, being in free acid form or salt form, or R 4 and R 5 together with the nitrogen atom to which they are attached form a heterocycle which may comprise other heteroatoms, R 6, R 8, R 9 and, when present, R 7 and R Io

  independently signify hydrogen, a hydro-

  C1-C8 carbon attached to the nitrogen atom through the

  mediator of an aliphatic carbon atom of this residue, or a hydrocarbon residue C 4 -C 8 interrupted by -O or -N R11-, a single substituent R 8, R 9 or Rlo can be interrupted by -N R11- R11 is hydrogen, methyl, ethyl or a group of the formula ## STR2 ## wherein R 12, R 13 and, when is present, R 14 independently signifies hydrogen or a methyl or ethyl group, or R 12 and R 13 together with the nitrogen atom to which they are attached form an aliphatic heterocycle containing 4 to 5 carbon atoms and m is an integer of 1 to 3; X is C 1 -C 6 alkylene, C 3 -C 6 hydroxyalkylene or C 4 -C 6 alkylene interrupted with -O-; and

  n is an integer from 0 to 20.

  Note that when a substituent R 7, R 10 or R 14 is present, the nitrogen atom with which it is associated will be in the form of quaternary ammonium, whereas when R 7, R 10 or R 14 is absent, the nitrogen atom

  in question will be in the normal trivalent form.

  According to a preferred embodiment of the invention, R 2 signifies hydrogen or a group

  methyl, ethyl or hydroxyethyl; R 3 means hydro

  gene; R 4 and R 5 independently represent a methyl, ethyl, propyl, butyl, hydroxyethyl, allyl or sulfoethyl group, or R 4 and R 5 together with the nitrogen atom to which they are attached form a piperidine ring; morpholine or pyrrolidine; X means a

  hydroxyalkylene group C 3 -C 6 and R 6 means hydro-

  gene or a C 1 -C 4 alkyl group and N is 0.

  According to a particular embodiment

  In a preferred embodiment of the invention, R 2 is hydrogen; R 4, R 5, R 6, R 8, R 9 and, when present, R 7 and R 10, independently signify a methyl group or

  ethyl; and X is a C 3 hydroxyalkylene group.

  The polymer to which the radicals of formula I

  are fixed to give the cationic polymer of the

  The polymer may be, for example, a polymer obtained by polycondensation.

  Examples of such a polymer include poly-

  esters, polyurethanes, polyamides and epoxy resins The cationic polymers of the invention may result from the polycondensation of a monomer

  already containing the remainder of formula I or the poly-

  condensation of a monomer containing a reactive group which can, after the polymerization, be converted into

  a remainder of formula I As other examples of poly-

  polysaccharides such as starch, cellulose, chitosan, guar gums and their derivatives. When the chosen polymer does not contain amide groups, these can be

  added according to methods known in the art.

  Such polymers may be modified by attachment of other groups. Particularly valid groups are polyoxyalkylene chains. Such groups generally consist entirely of oxyethylene units or comprise high proportions of such units. Said groups may modify the solubility characteristics in such units. water of the polymer and allow the use of the polymer in

special applications.

  According to a preferred embodiment of the invention, the polymers are addition polymers, that is to say polymers prepared by radical polymerization of an unsaturated monomer.

  ethylenic, preferably α, β-ethylenically unsaturated

  The addition polymers used according to the invention

  may be homopolymers or copolymers.

  They can be obtained using for the poly-

  The latter method is particularly useful, since the polymer can be a relatively inexpensive acrylamide polymer. The polymers which are especially useful are those which are especially useful in the preparation of a monomer comprising the appropriate radical of the formula I, or by fixing the radicals of the formula I on a polymer containing suitable reactive groups. homopolymers of acrylamide, but other monomers such as methacrylamide, ethacrylamide, N-methylmethacrylamide and N-hydroxyethylacrylamide

can be used.

  Interesting and useful polymers are

  those comprising both sequences of a poly-

  saccharide and sequences of an addition polymer.

  An example of such a polymer is that obtained by reacting starch with acrylamide and grafting.

of acrylamide by polyaddition.

  The molecular weight of the polymer can vary over a wide range and depends on the type of base polymer and the end use of the polymer. For example, when the polymer is to be used as a conditioning aid, the molecular weight will be between 1000 and 200. However, when the polymer is to be used as a dewatering aid, the molecular weight will be between

000 and 10,000,000.

  The remainder of formula I can be prepared according to methods known in the art. A particularly suitable method is the reaction of

  Mannich which can be carried out on a polymer containing

  appropriate reactive groups or on a monomer

  suitable prior to polymerization.

  The invention therefore relates to a process for the preparation of a polymer comprising radicals of formula I, said process comprising the reaction of

  Mannich amide groups of a monomer or a poly-

  mother, with an aldehyde and a secondary amine, and the

  quaternization of the product of the Mannich reaction.

  The Mannich reaction is a well known reaction of carbonyl compounds and is widely described

in the litterature.

  The Mannich reaction can be carried out on the monomer and then the Mannich reaction product thus obtained can be polymerized. However, it is also possible to first form a polymer comprising amide groups and then to subject said groups to

amides to the Mannich reaction.

  In particular, the invention relates to a process for the preparation of an addition polymer comprising monomer units comprising a remainder of formula I, said process being characterized in that a polymerizable monomer is subjected to the addition of formula II C Hz CHR 1 0.0 NHR 2 (II) o R 1 denotes hydrogen or a C 1 -C 6 alkyl or cycloalkyl group, a Mannich reaction with an aldehyde of formula R 3 CHO and a secondary amine of formula NR 4 R 5 H, the product of the Mannich reaction is quaternized and the monomer is polymerized by addition

  thus modified The monomer of formula II will preferably be

  the only monomer present to give a homopolymer. The aldehyde is preferably chosen from formaldehyde, acetaldehyde and propionaldehyde, especially formaldehyde. The amine NR 4 R 5 H is preferably chosen from dimethylamine,

  methylethylamine, hydroxyethylmethylamine, di-

  butylamine, piperidine, morpholine, pyrrolidine

  lidine, diethanolamine, diallylamine, acid

  N-methyl-aminoethanesulfonic acid and 2-amino-

  Propionitrile Especially preferred amines are dialkylamines such as diethylamine and dimethylamine. When the Mannich reaction has been carried out, the resulting monomer or monomeric unit will comprise a side chain of formula III ## STR1 ## The terminal nitrogen atom of this side chain may then quaternized before or after the polymerization to give polymers having radicals corresponding to formula I The quaternization can be carried out according to known methods, preferably by reaction with a compound of formula IV and / or V l + l YX ## STR1 ## wherein Y denotes a halogen and X is as defined above, or X and Y together mean a group of formula ZX 'o Z means an oxirane ring and X' means a C 1 -C 6 alkylene group, R 6, R 7, R 8, R 9 and, when present, Ro 10 have the meanings indicated above and A, when present, means an anion Halogen preferably means chlorine or bromine The anion A may be Any suitable anion, preferably a halide or methyl sulfate. Compounds IV and V may be different or, more commonly, may be identical. In place of the compound containing the oxirane ring, a secondary amine and a compound containing both a halogen and a cycle

  oxirane, for example epichlorohydrin.

  The Mannich reaction is carried out according to the usual methods, by adding aldehyde and amine in equimolar amounts. In place of the aldehyde, it is possible to add an aldehyde generating compound.

  paraformaldehyde, formalin and trioxymethane.

  The reaction is carried out at a temperature between 200 and 100 l C, preferably between 400 and 800 C, for 30 minutes to 10 hours, preferably for 1 hour.

at 3 o'clock.

  To this mixture is added the quaternary agent

  The quaternization reaction is carried out at a temperature between 400 and 1000 ° C, preferably between 400 and 700 ° C, and at a pH between 7 and 14, preferably between 7 and 10; the reaction time is between 30 minutes and 2 hours, preferably between 30 minutes and 1 hour. The pH H is then adjusted with a mineral acid to a value of between 1 and 4, preferably between 1 and 3. the terminal nitrogen atom of the remainder of formula I is quaternized, this quaternization can

  be carried out using another agent of quater-

  such as dimethyl sulphate.

  There are other methods for preparing the polymers of the invention, which are less preferred than those described above. For example, the monomer or polymer having the side chain of formula III can be reacted with epichlorohydrin and a secondary amine, to give

  a residue of formula I o X means -CH 2 CH (OH) CH 2-.

  According to another method, the monomer or the polymer respectively carrying the amide group or groups may be reacted in stages with formaldehyde, the compound of formula IV / V and the secondary amine. The Mannich reaction has valuable advantages, the main one being that the polymer obtained has uniformly distributed charges along the polymer backbone. Such polymers are different from those described, for example, in European Patent Application 0323847, the process described therein. A further advantage lies in the actual preparation of the polymer according to the process of the present invention. According to the state of the art, for example European Patent Application 0323847, a

  careful control of viscosity is often

  During the polymerization, on the other hand, the Mannich reaction of the process of the invention described above does not require such a control of the viscosity. The length of the remainder of formula I (the number n) can be controlled by choosing the quantity

  of quaternization agent and amine

  action, these substances will react to lengthen the rest until no more product can react. The polymers of the invention have many uses, especially in the paper industry where they can be used as additives, for example as flocculation agents, fixing agents, drippers and retention agents. be used as agents of

  flocculation in other areas such as

  minerals and the treatment of

  In addition to the properties which are as good as or even better than those of the products known in the art, they have the advantage of being obtained from relatively cheap raw materials. In addition, the polymers which contain starch present the advantage of using a raw material derived from a renewable source and moreover

  bio-degradable, which gives them a degree of bio-

degradability.

  The amount of cationic polymer in the

  vention used in commercial compositions

  depends on the nature of the composition and the use

  to which the polymer is intended.

  In each case, for example, for use with the paper pulp, the concentrations are in the range of 0.005 to 0.05%, preferably 0.01 to 0.05%. and 0.03% by weight of the pulp In the commercial compositions in which they are incorporated, the polymers of

  invention may be associated with other

  known ingredients, for example dyes, pigments, fillers, anti-foaming agents and surfactants. Such a composition will advantageously contain a stabilizer chosen from stabilizers known in the art, for example those

  described in British Patent 1,535,949.

  The following examples illustrate the present invention without in any way limiting its scope.

  these examples, the parties agree by weight.

Example 1

  42 parts of acrylamide monomer, 958 parts of water and 0.25 part of sodium salt of diethylene triamine pentaacetic acid (40% aqueous solution) are mixed and the pH 3 is adjusted with water. 36% hydrochloric acid The mixture is degassed with nitrogen for 1 hour, then heated to 400 ° C. and 2 parts of potassium persulfate are added.

  keep the temperature at 400 C for 3 hours.

  During this operation, the mixture is maintained under a nitrogen atmosphere. Then, 45.4 parts of formaldehyde (36% aqueous solution), 3.5 parts of trisodium phosphate and 950.2 parts of water are introduced and the mixture is heated. at 60 ° C. and maintained at this temperature for 1 hour. The temperature is raised to C, 54.2 parts of dimethylamine (58% aqueous solution) are added and the mixture is maintained at 70 ° C. for 1 hour. 70 C, and with stirring 105, 4 parts of epichlorohydrin and 108.3

  parts of dimethylamine (58% aqueous solution).

  After the addition, the mixture is maintained at 70 ° C. for 1 hour. The temperature is then reduced to C and the mixture is adjusted to 1-3 with 87.8.

  parts of 36% hydrochloric acid.

  The product obtained is a pale yellow viscous solution having a Brookfield RVT viscosity of

  2000 cps (20 C, spindle 5, 100 rpm).

Example 2

  This example describes the preparation of the

  polyacrylamide solution suitable for use in

in other examples.

  In a reaction vessel, portions of monomeric acrylamide, 950 parts of water and

  0.25 part of sodium salt of diethylene

  triamine-pentaacetic (40% aqueous solution) and

  adjusts the pH of the mixture to 3.0 with chloroacid

  After degassing with nitrogen for 1 hour, the mixture is heated to 40 ° C. and 3.5 parts of 2-propanol and 2.0 parts of potassium persulfate are added. The mixture is maintained at 40 ° C. for 30 hours. 3

hours under low nitrogen flow.

  The resulting polymer is in the form of a clear solution having a Brookfield RVT viscosity of 3000 cps (20 C, spindle 5, 100 rpm). Examples 3 to 6:

  Preparation of the polymers of the invention

  The materials used are as follows:

Example

n: (parts by weight)

4 5 6

  Polyacrylamide prepared according to Example 2 Water Trisodium phosphate Formaldehyde (36% aqueous solution)

Addition 1 of dimethyl

  amine (60% aqueous solution) Epichlorohydrin

Addition 2 of dimethyl

  amine (60% aqueous solution) Hydrochloric acid

(at 36%)

  786.2 3.5 16.2 16.1 17.9 14.5 13.6 3.5

1241.5

3.5 3.5

22.4 25.6 27.6

22.1 24.8, 3 28.4, 6, 5

, 1 23.0 27.6

27.1 40.7 54.2

  Polyacrylamide and water are mixed and trisodium phosphate and formaldehyde are added. The mixture is heated at 60 ° C. for 1 hour, then dimethylamine (addition 1) is added and the mixture is heated at 70 ° C. for 1 hour. The mixture is added and dimethylamine (addition 2) is added, followed by epichlorohydrin. The temperature is maintained at -25 ° C. for 30 minutes. The mixture is then heated at 80 ° C. for 1 hour and cooled to C. Hydrochloric acid is added. to get

a p H of 1-3.

  The polymers are obtained in the form of pale yellow viscous solutions having Brookfield RVT viscosities of 1000-2000 cps (20 C, spindle 5).

revolutions / min).

Example 7

  The procedure is as described in Example 4, except that, after heating the mixture at 80 ° C. for 1 hour, 41.58 parts of dimethyl sulphate are added. The mixture is stirred at 80 ° C. for a further 2 hours and cooled. at 20 C Added

  enough HCl to adjust p H to 1-3.

  The product is obtained in the form of a pale yellow viscous solution having a viscosity of

  3000 cps (20 C, spindle 5, 100 rpm).

Examples 8-12

Subjects Example n

8 9 10 11 12

  Polyacrylamide (60% solution of ex 2) 478 478 478 478 478 Water 1243.6 1431.6 1431.6 1243.6 1951

Tri-phase phosphate

  Sodium 3.5 3.5 3.5 3.5 3.5 Formaldehyde (aqueous solution

at 36%) 27.6 27.6 27.6 27.6 27.6

Quater- agent

  78,7 94,94 94,94 78,1 97,88 Dimethylamine (aqueous solution

60%) 27.6 27.6 27.6 27.6 27.6

  Dimethyl sulphate 41.58 41.58 The quaternizing agents used in the various examples are the following: Example 8 2-chloroethylamine hydrochloride (60% aqueous solution),

  Example 9 Dimethylamino Chloride Hydrochloride

ethyl (50% aqueous solution),

  EXAMPLE 10 Hydrochloride of Dimethylamino Chloride

  ethyl (50% aqueous solution), Example 11 2chloroethylamine hydrochloride (60% aqueous solution),

  Example 12 3-chloro-2-hydroxypropyltrichloride

  methylammonium (65% aqueous solution).

  The polyacrylamide solution is mixed with water, trisodium phosphate and formaldehyde are added and the mixture is heated at 60 ° C. for 1 hour. The quaternization agent is then added, the mixture is heated to 70 ° C. and is added to the mixture. maintained at 70 ° C. for 1 hour Dimethylamine is added and the mixture is maintained at 70 ° C. for a further 1 hour. In Examples 8, 9 and 12, the mixture is cooled to 25 ° C. and the pH is adjusted to 1-3 with 36% hydrochloric acid In Examples 9 and 10, dimethyl sulphate is added, the mixture is stirred for a further 1 hour at C, cooled and the pH is adjusted as indicated.

in Examples 8, 9 and 12.

  In each case, the product is obtained in the form of a pale yellow viscous liquid having a viscosity of 1000-2000 cps (20 C, spindle 5, 100 rpm).

Example 13

  573.7 parts of the polyacrylamide prepared in Example 2 are added. 45.4 parts of formaldehyde (39% aqueous solution), 3.5 parts of trisodium phosphate and 1195.1 parts of water are added. at 60 C and it is maintained at this

  temperature for 1 hour The temperature is then

  at 70 ° C. and 54.2 parts of dimethyl-

  amine (58% aqueous solution) The temperature is maintained

  at 700 ° C. for 1 hour. 94.4 parts of glycidyltrimethylammonium chloride are then added.

  maintains the temperature at 700 C for another hour.

  The mixture is then cooled to 200 ° C. and the

  p H to 1-3 with 36% hydrochloric acid.

  The product is obtained in the form of a pale yellow viscous solution having a viscosity of

  3000 cps (201 C, spindle 5, 100 rpm).

Example 14

  Use of a polymer of the invention

  as a dewatering agent in papermaking.

  A paste containing 1% of waste paper in water is prepared by treating 200 parts of cardboard and 200 parts of newspaper in 20,000 parts of water and then diluting with a further 1,000 parts of water. samples of 1000 parts of this paste, various amounts of the polymer of Example 1 are added and the time required for 700 parts of water to drip from the pulp through the mesh of a suitable sieve is carried out. the same way with the polymer of Example 1 of European Patent 0323847 and the product "Polymin" SK manufactured by BASF One part of each polymer solution is diluted with 19 parts of water to 1000 ml of paste is added 1, 2 , 3 and 4 parts of these solutions and the dewatering time is determined at

through the sieve.

The following results are obtained.

  Drip Time (in seconds) Product: Added Parts of Diluted Product

1 2 3 4

  Polymer of Example 1 60 38 23 17 Polymer of European Patent 0323847 60 39 23 16 "Polymin" SK 61 45 35 35 The results indicate a dewatering

  improved with respect to the "Polymin" SK and

  equivalent to the polymer of the patent

European 0323847.

Example 15

Use of a polysaccharide

  161 parts of wheat starch powder, 72 parts of acrylamide and 560 parts of water are mixed and the mixture is heated to 12-12.5 with a solution of sodium hydroxide. The mixture is then mixed for 2 hours at 600 ° C. while passing compressed air through the mixture. The mixture is then cooled and the pH is adjusted with acetic acid. 3.5 parts of trisodium orthophosphate are then added. 36% formaldehyde in water and homogeneously mixed The mixture is heated to 600 ° C. and maintained at this temperature for 1 hour. At the end of this period, 75 parts of 60% dimethylamine are added. in water, the temperature is raised to 700 C and held for 1 hour during this time, 92 parts are added

  of epichlorohydrin and 75 parts of 60% dimethylamine.

  The temperature is maintained at 700 ° C. for a further 1 hour after the addition is complete. The mixture is then cooled to 25 ° C. and the pH adjusted to 3 ° C.

  36% aqueous hydrochloric acid.

  The product is obtained in the form of a pale yellow viscous liquid having a viscosity of

  2000 cps (200 C, spindle 5, 100 rpm).

Example 16

  Use of a graft polymer starch / acrylamide.

  14.2 parts of mono acrylamide are mixed

  41.3 parts of water and 3.5 parts of corn starch were added and the pH was adjusted to 11.5 with sodium hydroxide solution. The mixture was stirred at 65 ° C. for 2 hours, It is then cooled and the pH is adjusted to 7.0 with acetic acid. To this mixture are added 531 parts of water, 0.15 part of diethylenetriamine-pentaacetic acid sodium salt (40% strength %) The mixture is mixed and adjusted to 3.5 with 36% hydrochloric acid solution. The mixture is degassed with nitrogen for 1 hour, then heated to 400 ° C. and added 0.12 g. Part of potassium persulfate The solution is maintained at 400 ° C. for 3 hours. During this operation, the reaction mixture is maintained under a nitrogen atmosphere. To this mixture is then added 216.7 parts of water and 2.5 parts of phosphate. trisodium and 19.3 parts of formaldehyde (aqueous solution at 38%) The mixture is heated at 600 C for 1 hour.

  at 700 ° C. and 22.4 parts of

  Methylamine (60% aqueous solution) The mixture is kept at 70 ° C. for 1 hour. At this temperature, 21.8 parts of epichlorohydrin and 22.4 ml of stirring are added to the stirred reaction mixture within 30 minutes.

  parts of dimethylamine (60% aqueous solution).

  After this addition, the mixture is maintained at 70 ° C. for 1 hour. The mixture is then cooled to 201 ° C. and the pH is adjusted to 1-3 with 87.8 parts of acid.

36% aqueous hydrochloric acid.

  The product is obtained as a pale yellow viscous solution having a Brookfield RVT viscosity of 1000 cps (spindle 5, 100 rpm at C).

Claims (9)

  A cationic polymer comprising at least one residue of formula I + 1 + 1 -CO-NR 2 -CHR 3 -NR 4 R 5 (X NR 6 1 R 7 1) X NR 8 R 1 -R-1-ol (1) wherein R 2 is hydrogen or R 4 defined below, R 3 is hydrogen or C 1 -C 3 alkyl, R 4 and R 5 are independently C 1 -C 6 alkyl, cycloalkyl, C 2 -C 6 alkenyl, aryl or aralkyl, said groups being optionally substituted by at least one group chosen from C 1 -C 6 hydroxyalkyl, C 1 -C 6 aminoalkyl and C 1 -C 6 sulphoalkyl groups; 6 and carboxy (C 1 -C 6) alkyl, the carboxy and sulfo groups, when present, being in free acid form or in salt form, or R 4 and R 5 together with the atom of to which they are attached, a heterocycle which may comprise other heteroatoms, R 6, R 8, R 9 and, when present, R 7 and Rio   independently signify hydrogen, a hydro-   carbon dioxide at C 1 -C 8 attached to the nitrogen atom   mediator of an aliphatic carbon atom of this residue, or a hydrocarbon residue C 4 -C 8 interrupted by -O or -N R11-, a single substituent R 8, R 9 or R Io can be interrupted by -N Rll R 1 is hydrogen, methyl, ethyl or a group of the formula I + 1 (CH 2) mNR 2 R 3 1 R 14 1 wherein R 12, R 13 and when present , R 14 independently signify hydrogen or a methyl or ethyl group, or R 12 and R 13 together with the nitrogen atom to which they are attached form an aliphatic heterocycle containing 4 to 5 carbon atoms and m means an integer of 1 to 3; X is C 1 -C 6 alkylene, C 3 -C 6 hydroxyalkylene or C 4 -C 6 alkylene interrupted with -O-; and   n is an integer from 0 to 20.   2 A cationic polymer according to the   1, characterized in that R 2 signifies hydro-   gene or a methyl, ethyl or hydroxyethyl group; R 3   means hydrogen; R 4 and R 5 stand independently   including methyl, ethyl, propyl, butyl, hydroxyethyl, allyl or sulfoethyl, or R 4 and R 5 together with the nitrogen atom to which they are attached form a piperidine, morpholine or pyrrolidine ring; X is a C 3 -C 6 hydroxyalkylene group and R 6 is hydrogen or C 1 -C 4 alkyl and n is means 0.   A cationic polymer according to the   1 or 2, characterized in that R 2 is hydrogen; R 4, R 5, R 6, R 8, R 6 and, when present, R 7 and R 10 independently signify a group methyl or ethyl.   4 A cationic polymer according to one   any of claims 1 to 3, characterized in that   than the polymer to which the remainder of formula (I) is fixed, is an addition polymer.   A cationic polymer according to claim 4, characterized in that the polymer   of addition is a polymer of acrylamide.   A cationic polymer according to one   any of claims 1 to 3, characterized in that   that the polymer comprises sequences of a poly-   saccharide and sequences of an addition polymer.   A process for preparing a cationic polymer according to claim 1, which comprises the Mannich reaction of the amide groups of a monomer or a polymer with an aldehyde and a secondary amine, and the quaternization of the   product resulting from the Mannich reaction.   A process for the preparation of a cationic polymer according to claim 7, characterized in that a polymerizable monomer is subjected to the addition of formula II 0 H 2-CHR,   (II) NHR 2 o R 1 denotes hydrogen or a C 1 -C 6 alkyl or cycloalkyl group, a Mannich reaction with an aldehyde of formula R 3 CHO and a secondary amine of formula NR 4 R 5 H the product of the Mannich reaction is quaternized and the monomer is polymerized by addition thus modified.   A composition adapted for use in the manufacture of paper, characterized in that it comprises a cationic polymer according to claim 1.   A composition according to claim 9, characterized in that the composition contains also a stabilizer.   A process for preparing paper, characterized in that it comprises the use of a   cationic polymer according to claim 1.